Polymers, substrates, methods for making such, and devices comprising the same

ABSTRACT

The present invention relates generally to substrates for making polymers and methods for making polymers. The present invention also relates generally to polymers and devices comprising the same.

RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. Provisional Application Ser. No. 61/761,499, filed Feb. 6, 2013, the disclosure of which is hereby incorporated by reference herein in its entirety.

FIELD

The present invention relates generally to substrates for making polymers and methods for making polymers. The present invention also relates generally to polymers and devices comprising the same.

BACKGROUND

Conjugated polymeric systems have been an area of research as some can provide conductive and light emitting and absorbing properties and thus have utility in electronics, molecular electronics and optoeletronics. Conjugated polymers have been made from various monomers and by various methods to yield a variety of polymers each with unique physical and electrical properties. These polymers include poly acetylenes, poly(pyrrole)s, polyanilines, polyazines, poly(p-phenylene vinylene), polycarbazoles, polyindoles, polyazepines poly(thiophene)s, poly(3,4-ethylenedioxythiophene), poly(p-phenylene sulfide), poly(fluorene)s, polyphenylenes, polypyrenes, polyazulenes, polynaphthalenes and polybenzimidazoles. These are generally linear polymers with variable chain lengths that are described in the literature.

Polyarylenes are a group of aromatic conjugated polymers that are branched and dendritic. Polyarylenes are made by the reaction of alkynes or with aromatic halides in the presence of metal catalysts. These are generally granular, globular or have a coil morphology. Variations of these polymers include polymers made with branched side chains or dendritic structures and polymers with branched monomers incorporated with more than one site for polymer extension. These later polymers result in branched polymers, where the conjugated backbone bifurcates. Each has unique electronic, optical and magnetic properties. However, because all of these reactions are unidirectional, all of the polymers eventually terminate, forming powders or microspheres and do not form a networked solid material.

The present invention addresses previous shortcomings in the art by providing polymers, substrates for making the polymers, methods for making such polymers, and devices comprising the same.

SUMMARY

Embodiments according to the invention are directed to substrates, polymers, methods, and devices. In some embodiments, a substrate of the present invention may be used to prepare a polymer of the present invention. Thus, in some embodiments provided is a substrate as described herein. Pursuant to these embodiments, provided herein is a polymer as described herein.

Also provided herein are methods for preparing a polymer of the present invention. One aspect of the present invention comprises a method of preparing a polyazine polymer comprising reacting an organic substrate comprising at least two aldehydes and/or ketones with a multiamine to form an organic polymer.

An additional aspect of the present invention comprises a method of preparing a cross-linked polyazine polymer comprising reacting an organic substrate comprising at least two aldehydes and/or ketones with a multiamine to form an organic polymer and oxidizing said organic polymer to form said cross-linked polyazine polymer.

In a further aspect of the present invention, provided is a device, such as, but not limited to, an electrochemical device, comprising a polymer of the present invention.

The foregoing and other aspects of the present invention will now be described in more detail with respect to other embodiments described herein. It should be appreciated that the invention can be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the synthesis of the following azadiene polymers (from top to bottom): 2,5-furan azadiene polymer, benzene-1,3-azadiene polymer, benzene-1,4-azadiene polymer, 4,4-biphenyl azadiene polymer, 2,3-naphthalene azadiene polymer, 2,5-thiophene azadiene polymer, 3,4-dimethyl-2,5-pyrrole azadiene polymer, and benzene-1,4-methyl azadiene polymer.

FIG. 2 shows the synthesis of a networked benzene-1,3,5-azadiene polymer using 1,3,5 benzene tricarboxaldehyde and hydrazine.

FIG. 3A shows a cyclic voltammetery of 3,4 dimethyl pyrrole azadiene linear conjugated polymer.

FIGS. 4A-J show an absorbance spectrum for A) benzene-1,3-azadiene polymer, B) 4,4-biphenyl azadiene polymer, C) 2,3-naphthalene azadiene polymer, D) 3,4 dimethyl-2,5-pyrrole azadiene polymer, E) benzene-1,3,5-azadiene network polymer, F) benzene-1,4-methyl azadiene polymer, G) benzene-1,3,5-methyl azadiene network polymer, H) indole-5-capped-2,5-furan azadiene polymer, I) crosslinked indole capped benzene-1,3,5-azadiene polymer oxidized with ammonium persulfate, J) crosslinked indole capped benzene-1,3,5-azadiene polymer oxidized with iron chloride.

FIG. 5 shows the indole capped 2,5 azadiene polymer polymer (bottom) and the final networked indole capped polymer after oxidation (top).

FIGS. 6A-C show A) the synthesis of an indole capped benzene-1,3,5-azadiene network polymer; B) shows this polymer prior to oxidation (left) and after oxidation (right) with ammonium persulfate to produce an indole crosslinked benzene 1,3,5-azadiene network polymer; C) shows an absorption spectrum for the oxidized cross-linked indole capped 1,3,5 benzene azadiene polymer; and D) shows a cyclic voltammogram of the polymer.

FIG. 7 shows the synthesis of the following multifunctional substrates (from top to bottom): 3-indole azadiene, thianaphthene-3-azadiene, 5-indole azadiene, and 3-pyrrole azadiene.

DETAILED DESCRIPTION

The present invention will now be described more fully hereinafter. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the present application and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety for the teachings relevant to the sentence and/or paragraph in which the reference is presented. In case of a conflict in terminology, the present specification is controlling.

Also as used herein, “and/or” refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (“or”).

Unless the context indicates otherwise, it is specifically intended that the various features of the invention described herein can be used in any combination.

Moreover, the present invention also contemplates that in some embodiments of the invention, any feature or combination of features set forth herein can be excluded or omitted. To illustrate, if the specification states that a complex comprises components A, B and C, it is specifically intended that any of A, B or C, or a combination thereof, can be omitted and disclaimed.

As used herein, the transitional phrase “consisting essentially of” (and grammatical variants) is to be interpreted as encompassing the recited materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention. See, In re Herz, 537 F.2d 549, 551-52, 190 U.S.P.Q. 461, 463 (CCPA 1976) (emphasis in the original); see also MPEP §2111.03. Thus, the term “consisting essentially of” as used herein should not be interpreted as equivalent to “comprising.”

The term “about,” as used herein when referring to a measurable value, such as an amount or concentration and the like, is meant to refer to variations of up to ±20% of the specified value, such as, but not limited to, ±10%, ±5%, ±1%, ±0.5%, or even ±0.1% of the specified value, as well as the specified value. For example, “about X” where X is the measurable value, can include X as well as a variation of ±20%, ±10%, ±5%, ±1%, ±0.5%, or ±0.1% of X. A range provided herein for a measurable value may include any other range and/or individual value therein.

It will be understood that when an element or layer is referred to as being “on,” “connected to,” or “coupled with” another element or layer, it can be directly on, connected, or coupled with the other element or layer or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly connected to,” or “directly coupled with” another element or layer, there are no intervening elements or layers present.

“Moiety” or “moieties,” as used herein, refer to a portion of a molecule, such as a portion of a substrate, typically having a particular functional or structural feature, For example, a moiety may comprise a linking group (a portion of a molecule connecting at least two other portions of the molecule). In some embodiments, a moiety may be a reactive portion of a substrate.

“Substituted” as used herein to describe a chemical structure, group, or moiety, refers to the structure, group, or moiety comprising one or more substituents. As used herein, in cases in which a first group is “substituted with” a second group, the second group is attached to the first group whereby a moiety of the first group (typically a hydrogen) is replaced by the second group. The substituted group may contain one or more substituents that may be the same or different.

“Substituent” as used herein references a group that replaces another group in a chemical structure. Typical substituents include nonhydrogen atoms (e.g., halogens), functional groups (such as, but not limited to, amino, sulfhydryl, carbonyl, hydroxyl, alkoxy, carboxyl, silyl, silyloxy, phosphate and the like), hydrocarbyl groups, and hydrocarbyl groups substituted with one or more heteroatoms. Exemplary substituents include, but are not limited to, alkyl, lower alkyl, halo, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, heterocyclo, heterocycloalkyl, aryl, arylalkyl, lower alkoxy, thioalkyl, hydroxyl, thio, mercapto, amino, imino, halo, cyano, nitro, nitroso, azido, carboxy, sulfide, sulfone, sulfoxy, phosphoryl, silyl, silylalkyl, silyloxy, boronyl, and modified lower alkyl.

“Alkyl” as used herein alone or as part of another group, refers to a linear (“straight chain”), branched chain, and/or cyclic hydrocarbon containing from 1 to 30 or more carbon atoms. In some embodiments, the alkyl group may contain 1, 2, or 3 up to 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like. “Lower alkyl” as used herein, is a subset of alkyl and refers to a straight or branched chain hydrocarbon group containing from 1 to 4 carbon atoms. Representative examples of lower alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, and the like. The term “alkyl” or “loweralkyl” is intended to include both substituted and unsubstituted alkyl or loweralkyl unless otherwise indicated and these groups may be substituted with groups such as, but not limited to, polyalkylene oxides (such as PEG), halo (e.g., haloalkyl), alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclo, heterocycloalkyl, hydroxyl, alkoxy (thereby creating a polyalkoxy such as polyethylene glycol), alkenyloxy, alkynyloxy, haloalkoxy, cycloalkoxy, cycloalkylalkyloxy, aryloxy, arylalkyloxy, heterocyclooxy, heterocyclolalkyloxy, mercapto, alkyl-S(O)_(m), haloalkyl-S(O)_(m), alkenyl-S(O)_(m), alkynyl-S(O)_(m), cycloalkyl-S(O)_(m), cycloalkylalkyl-S(O)_(m), aryl-S(O)_(m), arylalkyl-S(O)_(m), heterocyclo-S(O)_(m), heterocycloalkyl-S(O)_(m), amino, carboxy, alkylamino, alkenylamino, alkynylamino, haloalkylamino, cycloalkylamino, cycloalkylalkylamino, arylamino, arylalkylamino, heterocycloamino, heterocycloalkylamino, disubstituted-amino, acylamino, acyloxy, ester, amide, sulfonamide, urea, alkoxyacylamino, aminoacyloxy, nitro or cyano, where m=0, 1, 2 or 3.

“Alkenyl” as used herein alone or as part of another group, refers to linear (“straight chain”), branched chain, and/or cyclic containing from 1 to 30 or more carbon atoms (or in loweralkenyl 1 to 4 carbon atoms) which include 1 to 10 or more double bonds in the hydrocarbon chain. In some embodiments, the alkenyl group may contain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms. Representative examples of alkenyl include, but are not limited to, methylene (═CH₂), vinyl (—CH═CH₂), allyl (—CH₂CH═CH₂), 2-butenyl, 3-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2,4-heptadiene, and the like. The term “alkenyl” or “loweralkenyl” is intended to include both substituted and unsubstituted alkenyl or loweralkenyl unless otherwise indicated and these groups may be substituted with groups such as those described in connection with alkyl and loweralkyl above.

“Conjugated,” as used herein, refers to a moiety or compound comprising at least two double bonds with a single bond between the two double bonds. Thus, a conjugated compound comprises two double bonds that alternate with a single bond. For example, a diene may be conjugated. Conjugated dienes comprise double bonds on adjacent carbons; that is, the two double bonds are separated by one single bond. In a conjugated diene, there are four adjacent triagonal, sp²-hybridized carbons. Each carbon bears a p orbital comprising one electron. Not only does the pair of p orbitals of each double bond overlap to form pi-bonds, but there is also some overlap across the formal carbon-carbon single bond.

Examples of conjugated double bonds are depicted below:

A further example of a conjugated moiety and/or compound is one that comprises two or more nitrogen atoms within the conjugated system as illustrated below:

In certain embodiments, a conjugated moiety or compound may be aromatic. The term “aryl” is used herein to refer to an aromatic moiety or compound. “Aryl” may be a single aromatic ring or multiple aromatic rings that are fused together, linked covalently, or linked to a common group, such as, but not limited to, a methylene or ethylene moiety. The common linking group also may be a carbonyl, as in benzophenone, or oxygen, as in diphenylether, or nitrogen, as in diphenylamine. The term “aryl” specifically encompasses heterocyclic aromatic compounds. The aromatic ring(s) may comprise phenyl, naphthyl, tetrahydronaphthyl, biphenyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, thienyl, furyl, pyrazinyl, pyrrolyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone, among others. In particular embodiments, the term “aryl” means a cyclic aromatic comprising about 5 to about 50 or more carbon atoms, and includes 5- and 6-membered hydrocarbon and heterocyclic aromatic rings.

In some embodiments, a substrate of the present invention may comprise a conjugated moiety and/or may be conjugated. In some embodiments, a substrate of the present invention may comprise an aromatic moiety and/or may be aromatic.

“Multiamine,” as used herein, refers to a compound comprising two or more amines. A multiamine may comprise 2, 3, 4, 5, 6, 7, or more amines. A multiamine may comprise two or more terminal and/or pendant amine groups that may be primary amine groups. In some embodiments, a multiamine comprises two amines and thus is a diamine. In some embodiments, a multiamine comprises three amines and thus is a triamine. Exemplary multiamines include, but are not limited to, hydrazine, triaminobenzene, ethylenediamine, and any combination thereof.

“Monocarbonyl compound,” as used herein, refers to a compound comprising only one carbonyl group. A monocarbonyl compound can comprise an aldehyde (i.e., a monoaldehyde) or a ketone (i.e., a monoketone). In some embodiments, a monocarbonyl compound has the following structure

wherein

R is a conjugated and/or aromatic moiety; and

R¹ is selected from the group consisting of hydrogen, alkyl, and an alkylene.

According to some embodiments of the present invention, provided herein are substrates that may be used to prepare a conjugated polymer. “Substrate,” as used herein, refers to a compound that can be polymerized to form a polymer. A substrate may be polymerized using chemical oxidative polymerization, enzymatic oxidative polymerization, and/or a condensation reaction. In some embodiments, a substrate and/or a polymer may be acted on by an enzyme. For example, a substrate may be oxidized by an enzyme. In other embodiments, a substrate may not be acted on by an enzyme. In some embodiments, the enzyme may be an oxidase. “Oxidase,” as used herein, refers to an enzyme that oxidizes a substrate. Exemplary oxidases include, but are not limited to, phenol oxidase, a polyphenol oxidase, a catechol oxidase, a tyrosinase, a laccase, monophenol monooxygenase, phenolase, monophenol oxidase, cresolase, monophenolase, tyrosine-dopa oxidase, monophenol monooxidase, monophenol dihydroxyphenylalanine:oxygen oxidoreductase, N-acetyl-6-hydroxytryptophan oxidase, dihydroxy-L-phenylalanine oxygen oxidoreductase, o-diphenol:O₂ oxidoreductase, catecholase, o-diphenol oxidase, monophenol oxidase, cresolase, and any combination thereof.

In some embodiments, a substrate and/or polymer may be polymerized using an oxidizing agent. Exemplary oxidizing agents include, but are not limited to, ammonium persulfate, iron (III) chloride, hydrogen peroxide, urea peroxide, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, potassium percarbonate, potassium persulfate, sodium persulfate, ferric nitrate, diammonium cerium nitrate, iron sulfate, ozone, potassium periodate, and any combination thereof.

A substrate may be a synthetic substrate or a natural substrate, either of which may be polymerized using chemical oxidative polymerization and/or enzymatic oxidative polymerization. “Synthetic,” as used herein in reference to a substrate, refers to a substrate that is not a natural substrate of an oxidase. Thus, a synthetic substrate is not found in nature as a substrate for an oxidase and thus is an unnatural substrate. In some embodiments, a synthetic substrate may be synthetically prepared, and optionally one or more compounds may be obtained or derived from nature and used to synthetically prepare a synthetic substrate.

“Natural,” as used herein in reference to a substrate, refers to a substrate that is a natural substrate of an oxidase. Thus, a natural substrate is found in nature as a substrate for an oxidase. In some embodiments, a natural substrate may be synthetically prepared, and optionally one or more compounds may be obtained or derived from nature and used to synthetically prepare a natural substrate.

“Organic,” as used herein, refers to a compound, substrate, and/or polymer comprising carbon. In some embodiments, an organic substrate may comprise a metal, such as, but not limited to copper, gold, aluminum, lithium, calcium, sodium, tungsten, zinc, iron, platinum, tin, magnesium, lead, titanium, potassium, silver, rubidium, and any combination thereof. In certain embodiments, an organic substrate is exposed, contacted, and/or doped with a metal and/or metal containing compound such that the metal becomes incorporated with the substrate and/or forms a complex with the substrate.

In certain embodiments, a substrate of the present invention is multifunctional. “Multifunctional,” as used herein in reference to a substrate, refers to an organic substrate that comprises at least two moieties that are configured to provide polymerization in more than one direction. A multifunctional organic substrate may comprise 2, 3, 4, 5, or more moieties that may be the same and/or different. In some embodiments, a multifunctional substrate may be a synthetic substrate. In other embodiments, a multifunctional substrate may be a natural substrate. Exemplary multifunctional organic substrates include, but are not limited to, those shown in Scheme 1.

In some embodiments, a multifunctional organic substrate comprises at least two reactive moieties. In certain embodiments, a multifunctional organic substrate comprises at least three reactive moieties. “Reactive moiety” and “reactive moieties,” as used herein, refer to moieties that can be oxidized by an oxidase and/or an oxidizing agent. Exemplary reactive moieties include, but are not limited to, an indole, a pyrrole, a catechol, a tyrosyl, a catecholamine, thianaphthene, derivatives thereof, and any combination thereof. In certain embodiments, a substrate comprises one or more reactive moieties selected from the group consisting of a 6-hydroxyindole, a 5-hydroxyindole, a 5,6-dihydroxyindole, derivatives thereof, and any combination thereof. “Derivative” and grammatical variations thereof, as used herein, refer to a compound that is formed from, or can be regarded as formed from, a structurally related compound. In some embodiments, a derivative may be attached to and/or a portion of a compound. Thus, a derivative may refer to a moiety attached to a parent compound and thus one or more of groups of the moiety (generally hydrogen atoms) may be removed in order to attach the moiety to the parent compound. For example, substrate 1 of Scheme 1 shows two indole derivatives that are each separately attached to the parent compound.

In certain embodiments, a reactive moiety may comprise a conjugated moiety. A substrate of the present invention may comprise one or more, such as 2, 3, 4, or more, reactive moieties each of which may comprise a conjugated moiety. In some embodiments, a reactive moiety may comprise an aromatic moiety. A substrate of the present invention may comprise one or more, such as 2, 3, 4, or more, reactive moieties each of which may comprise an aromatic moiety.

As those skilled in the art will recognize, a polymerization reaction may occur or involve one or more reactive sites within a moiety. Thus, a reactive moiety may have at least 2, 3, 4, 5, 6, 7, 8, 9, 10, or more reactive sites. For example, as shown in Scheme 2, for 5,6-dihydroxyindole, polymerization may occur or take place at the C2, C3, C4, and/or C7 position, and a bond may be created between at least one of these reactive sites and at least one reactive site of another reactive moiety.

A reactive site within a moiety of a substrate of the present invention may be modified and/or blocked with a substituent, such as, but not limited to an alkyl. This may cause a polymerization reaction to occur or involve one or more different reactive sites within a reactive moiety of a substrate.

A substrate of the present invention may comprise two or more reactive moieties that may be joined by a linker. “Linker” as used herein refers to a moiety that serves as a point of attachment for two or more reactive moieties that may be same and/or different. Two or more reactive moieties may be bound covalently to a linker or may be fused to a linker. A linker may be a conjugated moiety, and in some embodiments a linker may be an aromatic moiety. In certain embodiments, a method of the present invention may result in a linker becoming conjugated. For example, polymerization of a substrate using either an oxidase or an oxidizing agent may result in a conjugated linker.

In some embodiments, a substrate of the present invention is monomeric. “Monomeric,” as used herein in reference to a substrate, refers to a substrate that has not been linked or bound to another substrate. Thus, the substrate is not oligomeric or polymeric. While a substrate may have one or more of the same moieties within the substrate, a monomeric substrate does not comprise two or more substrates that have been linked together. For example, the substrates provided in Scheme 1 are monomeric as they have not been linked to another substrate.

In some embodiments, a substrate of the present invention comprises a substrate as described herein. In certain embodiments, a substrate of the present invention comprises a substrate provided in Scheme 1 and/or a substrate described in the examples provided herein. A substrate of the present invention may be used to prepare a polymer of the present invention. In some embodiments, a substrate, which may be a multifunctional organic substrate that may be synthetic, may comprise a conjugated moiety having two or more reactive moieties attached. The conjugated moiety may comprise a —C═N—N═C— unit and/or an aryl. “Unit” as used herein is used interchangeably with the term “segment”. The two or more reactive moieties may be the same and/or different and may comprise an indole derivative, a pyrrole derivative, a catechol derivative, a tyrosyl derivative, a thianaphthene derivative, and/or a catecholamine derivative. In some embodiments, the substrate may comprise three reactive moieties. In some embodiments, a reactive moiety may be attached to the conjugated moiety via a linker that may be conjugated.

In some embodiments, a polymer of the present invention comprises a polymer as described herein. In certain embodiments, a polymer of the present invention comprises a polymer described in the examples provided herein, such as, but not limited to, a polymer provided in Table 1. A method of the present invention may be used to prepare a polymer of the present invention. In some embodiments, a substrate of the present invention may be used in a method of the present invention to prepare a polymer of the present invention.

A polymer of the present invention may be networked.

“Networked,” as used herein in reference to a polymer of the present invention, refers to a cross-linked polymer (i.e., a polymer comprising one or more polymer chains that are linked together either directly through covalent attachment and/or through a moiety or group), wherein the polymer chains of the cross-linked polymer are interconnected at two or more locations within the polymer chains. In some embodiments, the cross-links (i.e., the linkages connecting the one or more polymer chains) in a networked polymer of the present invention comprise a conjugated moiety. In certain embodiments, a cross-linked and/or networked polymer of the present invention may comprise a —C═N—N═C— unit and/or a —C═N—R—N═C— unit, where R is a conjugated moiety and/or an aryl. In some embodiments, one or more cross-links of a cross-linked and/or networked polymer of the present invention may comprise a unit and/or a —C═N—R—N═C— unit, where R is a conjugated moiety and/or an aryl.

According to some embodiments of the present invention, provided is a method of preparing a polyazine polymer comprising reacting an organic substrate comprising at least two aldehydes and/or ketones with a multiamine to form an organic polyazine polymer. The method may further comprise oxidizing said organic polyazine polymer to form a cross-linked polyazine polymer. The oxidizing step may be carried out by enzymatic oxidative polymerization with an oxidase and/or by chemical oxidative polymerization with an oxidizing agent. The organic substrate may be a natural or synthetic substrate.

In some embodiments, the organic substrate may be a dialdehyde and/or a trialdehyde and the multiamine may be a diamine and/or a triamine. Exemplary reaction schemes between a diamine and a dialdehyde are shown in Scheme 3, where R is a conjugated moiety and/or an aryl and n is a number from 2 to 1,000,000.

Thus, a polyazine polymer, which may be cross-linked and/or networked, may comprise a unit having a structure of one or more of:

wherein R is a conjugated moiety and/or an aryl.

Further exemplary reaction schemes between a dialdehyde and/or trialdehyde and a diamine and/or triamine are shown in Scheme 4, where R and R′ are each independently a conjugated moiety and/or an aryl and n is a number from 2 to 1,000,000.

Thus, a polyazine polymer, which may be cross-linked and/or networked, may comprise a unit having a structure of one or more of:

wherein R and R′ are each independently a conjugated moiety and/or an aryl.

An organic substrate comprising at least two aldehydes and/or ketones may comprise a conjugated moiety. In some embodiments, an organic substrate comprising at least two aldehydes and/or ketones may comprise an aromatic moiety. Optionally, the at least two aldehydes and/or ketones may be attached and/or bound to the aromatic moiety. In some embodiments, an organic substrate may have the structure of Formula (I):

wherein

R is a conjugated and/or aromatic moiety; and

R¹ and R² are each independently selected from the group consisting of hydrogen, alkyl, and alkenyl. An organic polymer prepared using a substrate having a structure of Formula (I) may have a structure comprising (RC(R¹)NNCR²)_(n)RC(O)R¹, (RC(R¹)NNCR²)_(n)RC(O)R², or (RC(R¹)NNCR²)_(n)CNN, wherein n is a number from 2 to 1,000,000 and R¹ and R² are each independently selected from the group consisting of hydrogen, alkyl, and alkenyl.

An organic substrate according to some embodiments may comprise at least three aldehydes and/or ketones, and may in some embodiments react with a multiamine to form a networked organic polyazine polymer. In some embodiments, an organic substrate may have the structure of Formula (II):

wherein

R is a conjugated and/or aromatic moiety; and

R¹, R², and R³ are each independently selected from the group consisting of hydrogen, alkyl, and alkenyl. An organic polymer prepared using a substrate having a structure of Formula (II) may have a structure comprising ((RC(R¹)NNCR¹)(RC(R²)NNCR²)(RC(R³)NNCR³))_(n)RC(O)R¹, ((RC(R¹)NNCR¹)(RC(R²)NNCR²)(RC(R³)NNCR³))_(n)RC_(n)RC(O)R², ((RC(R)NNCR¹)(RC(R²)NNCR²)(RC(R³)NNCR³))_(n)RC_(n)RC(O)R³, or ((RC(R¹)NNCR¹)(RC(R²)NNCR²)(RC(R³)NNCR³))_(n)RC_(n)CNN, wherein n is a number from 2 to 1,000,000 and R¹, R², and R³ are each independently selected from the group consisting of hydrogen, alkyl, and alkenyl

In certain embodiments, an organic substrate may comprise an indole, a pyrrole, a phenol, a thiophene, a furan, a thianaphthene, an acetylene, a catechol, a tyrosyl, a catecholamine, a phenyl, a benzene, a naphthalene, a biphenyl, derivatives thereof, and any combination thereof. In some embodiments, an organic substrate comprises an indole or a derivative thereof and/or a pyrrole or a derivative thereof that may be substituted with at least two aldehydes and/or ketones.

In some embodiments, a method of preparing a polyazine polymer may comprise reacting an organic substrate comprising at least two aldehydes and/or ketones with a multiamine to form an organic polyazine polymer and reacting the organic polyazine polymer with a second organic substrate comprising at least two aldehydes and/or ketones and a multiamine to form a second organic polyazine polymer. In some embodiments, the second organic substrate is different than the first organic substrate and thus a heteropolymer may be formed. “Heteropolymer” as used herein refers to an organic polymer comprising two or more different polymeric units. The method may further comprise oxidizing the second organic polyazine polymer to form a cross-linked polyazine polymer.

Prior to or concurrently with one or more steps in a method of preparing a polyazine polymer, such as, but not limited to, a cross-linked polyazine polymer, a metal may be added to the substrate and/or reaction mixture. Thus, a substrate, organic polyazine polymer, and/or cross-linked polyazine polymer may be doped with a metal, ionic liquid, ionomer, and/or the like. In some embodiments, doping a substrate, organic polyazine polymer, and/or cross-linked polyazine polymer with a metal may increase the electrical properties of the organic polyazine polymer and/or cross-linked polyazine polymer. In certain embodiments, the oxidizing step is carried out with a reagent, such as, but not limited to, iron (III) chloride, ammonium persulfate, hydrogen peroxide, urea peroxide, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, potassium percarbonate, potassium persulfate, sodium persulfate, ferric nitrate, diammonium cerium nitrate, iron sulfate, ozone, potassium periodate, and any combination thereof, that may oxidize the organic polyazine polymer and/or dope the organic polyazine polymer and/or cross-linked polyazine polymer.

In some embodiments, a method of preparing a cross-linked polyazine polymer may comprise reacting a monocarbonyl compound with the organic polyazine polymer and a multiamine prior to the oxidizing step. Reaction of the organic polyazine polymer with a multiamine and monocarbonyl compound can result in a capped organic polyazine polymer, meaning that the monocarbonyl compound may be added onto the end of one or more of the polymer chains. In some embodiments, a monocarbonyl compound has the structure

wherein

R is a conjugated and/or aromatic moiety; and

R¹ is selected from the group consisting of hydrogen, alkyl, and alkenyl.

A substrate of the present invention and/or a method of the present invention may provide a conjugated organic polymer, which may be cross-linked and/or networked. In some embodiments, a substrate of the present invention and/or a method of the present invention may provide an organic polyazine polymer, which may be cross-linked and/or networked. A polyazine polymer of the present invention may itself be novel and/or may have novel electrical and/or light emitting and/or light absorbing properties. In some embodiments, a polyazine polymer of the present invention does not include a 2,5-furan azadiene polymer, a 2,5-thiophene azadiene polymer, benzene-1,4-dicarboxaldehyde, and/or a 1,4-benzene azadiene polymer. A polymer of the present invention (e.g., a polyazine polymer, cross-linked polyazine polymer, etc.) may have an energy band gap of less than about 3 eV, such as, but not limited to, an energy band gap of about 0 to about 2.75 eV, about 1 to about 2.5 eV, or about 1.5 to about 2 eV.

According to further embodiments of the present invention, provided is an electrochemical device comprising a polymer of the present invention, such as, but not limited to, a polyazine polymer and/or a cross-linked polyazine polymer. An electrochemical device according to embodiments of the invention may comprise a working electrode, a counter electrode, and a polymer of the present invention (e.g., a polyazine polymer and/or cross-linked polyazine polymer), wherein said working electrode is in operative communication with said counter electrode, and the polymer is in operative communication with said working electrode or said counter electrode. In certain embodiments, the polymer may be conjugated, and may optionally comprise a metal. The polymer may have an energy band gap of less than about 3 eV.

In some embodiments, a polymer of the present invention (e.g., a polyazine polymer and/or cross-linked polyazine polymer) is disposed on at least a portion of a working electrode. The polymer may be directly or indirectly in contact with at least a portion of a working electrode. In certain embodiments, a polymer of the present invention (e.g., a polyazine polymer and/or cross-linked polyazine polymer) may be interposed between a working electrode and a counter electrode. In some embodiments, an electrochemical device comprises a polymer of the present invention (e.g., polyazine polymer and/or cross-linked polyazine polymer) that may be in the form of a coating in contact with or on a working electrode and/or a counter electrode.

An electrochemical device of the present invention encompasses all types of devices to perform electrochemical reactions, including, but not limited to, photovoltaic reactions. Exemplary electrochemical devices include, but are not limited to, a battery; a fuel cell; a solar cell; a light emitting diode including an organic light emitting diode; a light emitting electrochemical cell; a transistor; a photo-conductor drum; a memory device; a capacitor including a supercapacitor, an ultracapacitor, and/or an electric double-layer capacitor; a radio frequency identification device (RFID); or a device formed of a combination thereof; and any combination thereof. In some embodiments, light emitting diode comprises a polymer of the present invention (e.g., polyazine polymer and/or cross-linked polyazine polymer).

The present invention is explained in greater detail in the following non-limiting Examples.

EXAMPLES Example 1

Polyazine polymers were synthesized as follows. 0.2 g of various dicarboxaldehydes were reacted with 0.03 g of hydrazine monohydrate (65%) or 0.1 g triaminobenzene in 15 ml of ethanol or acetonitrile to yield azadiene polymers (Table 1). In some cases, as with ketones, the PH was adjusted to about 5.0. In some cases these polymers were further modified (i.e., capped) by addition of indole or pyrrole moieties on the ends of the polymer chain by reacting the washed azadiene polymer with an 0.1 g of indole aldehydes or pyrrole aldehydes and 0.015 g of hydrazine monohydrate (15%) in 5 ml of ethanol or acetonitrile as described in Table 1. These resulted in capped polymers with the ends capped with one or more indole or pyrrole groups. Some of the capped polymers were subsequently crosslinked with an excess of 0.8 M ammonium persulfate.

For some of the polymers, the resistivity, HOMO/LUMO, band gap and state were determined (Table 2). For resistivity, polymers were doped with iodine vapors in a sealed chamber for up to seven days. Resistivity was measured by the 2-point method using a keithley Model 2110-120-GPIB digital multimeter.

Orbital energy levels were measured with a Bio-Logic SP-150 potentiostat using a silver/silver chloride reference electrode, platinum counter electrode, and a glassy carbon working electrode. Potentials were referenced with respect to ferrocene. The working solution was degassed under argon with 0.1 M tetrabutylammonium hexafluorophospate in acetonitrile as the supporting electrolyte. Potentials were measured in solution and also as thin films where possible.

UV-vis absorbance was also measured for some of the polymers. Polymers were dissolved in an appropriate solvent(s) including either water, N,N-dimethyl formamide, dimethyl sulfoxide, cresol, N-methyl-2-pyrrolidone, or acetonitrile. Absorbance was measured with a Shimadzu UV mini 1240 over a range of 200-1100 nm wavelength calibrated with the appropriate solvent for each polymer.

The polymer structures are depicted in Scheme 5.

FIG. 1 shows the synthesis of the azadiene polymers. FIG. 2 shows the synthesis of a networked benzene-1,3,5-azadiene polymer using 1,3,5 benzene tricarboxaldehyde and hydrazine. FIG. 3 shows a cyclic voltammetery of 3,4 dimethyl pyrrole azadiene linear conjugated polymer. FIGS. 4A-J show an absorbance spectrum for A) benzene-1,3-azadiene polymer, B) 4,4-biphenyl azadiene polymer, C) 2,3-naphthalene azadiene polymer, D) 3,4 dimethyl-2,5-pyrrole azadiene polymer, E) benzene-1,3,5-azadiene network polymer, F) benzene-1,4-methyl azadiene polymer, G) benzene-1,3,5-methyl azadiene networked polymer, H) indole-5-capped-2,5-furan azadiene polymer, 1) crosslinked indole capped benzene-1,3,5-azadiene polymer oxidized with ammonium persulfate, J) crosslinked indole capped benzene-1,3,5-azadiene polymer oxidized with iron chloride.

TABLE 1 Synthetic details for preparing polyazine polymers. Cross- Capping Capping linking Reactant 1 Reactant 2 Solvent Product Reactant 1 reactant 2 Solvent Product reactant 2,5-furan Hydrazine Ethanol 2,5-furan azadiene dicarboxaldehyde polymer 2,5-furan Hydrazine Ethanol 2,5-furan azadiene Indole-5- Hydrazine acetonitrile indole capped Ammonium dicarboxaldehyde polymer carboxaldehyde furan-2,5,- persulfate azadiene polymer 2,5-furan Hydrazine Ethanol 2,5-furan azadiene Pyrrole-2- Hydrazine acetonitrile Pyrrole capped Ammonium dicarboxaldehyde polymer carboxaldehyde furan-2,5,- persulfate azadiene polymer Benzene-1,3- Hydrazine Ethanol Benzene-1,3- dicarboxaldehyde azadiene polymer Benezene-1,4- Hydrazine Ethanol Benzene-1,4- dicarboxaldehyde azadiene polymer 4,4-biphenyl Hydrazine Ethanol, 4,4-biphenyl dicarboxaldehyde acetonitrile azadiene polymer 2,3-naphthalene Hydrazine Ethanol, 2,3-naphthalene dicarboxaldehyde acetonitrile azadiene polymer 2,5-thiophene Hydrazine Ethanol 2,5-thiophene dicarboxaldehyde azadiene polymer 3,4-dimethyl-2,5- Hydrazine Ethanol 3,4-dimethyl-2,5- pyrrole pyrrole azadiene dicarboxaldehyde polymer Benzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5- tricarboxaldehyde acetonitrile azadiene network polymer Benzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5- 5-carboxyindole Hydrazine acetonitrile Indole capped tricarboxaldehyde acetonitrile azadiene network Benzene-1,3,5- polymer azadiene network polymer Benzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5- 5-carboxyindole Hydrazine acetonitrile Indole capped Ammonium tricarboxaldehyde acetonitrile azadiene network Benzene-1,3,5- persulfate polymer azadiene network polymer Benzene-1,3,5- Hydrazine Ethanol, Benzene-1,3,5- 5-carboxyindole Hydrazine acetonitrile Indole capped Iron tricarboxaldehyde acetonitrile azadiene network Benzene-1,3,5- Chloride polymer azadiene network (FeCl₃) polymer Benzene-1,3,5- Triaminobenzene Ethanol, Benzene-imine tricarboxaldehyde acetonitrile network polymer 1,4-diacetyl Hydrazine Ethanol Benzene-1,4- benzene methyl azadiene polymer 1,3,5-triacetyl Hydrazine Ethanol, Benezene-1,3,5- benzene acetonitrile methyl azadiene network polymer

TABLE 2 Resistivity, HOMO/LUMO, band gap and state information. HOMO/LUMO BandGap Product Resistivity (eV) (eV) State Benzene-1,3-azadiene polymer 50 Mohms −5.96/−2.86 3.1 film 4,4-biphenyl azadiene polymer 35 Mohms 3,4-dimethyl-2,5-pyrrole azadiene polymer 10 Mohms −5.51/−3.43 2.08 solution Indole-5 capped 2,5-furan azadiene polymer −3.44/−6.12 2.68 solution 2,3-naphthalene azadiene polymer −3.66/−5.34 1.68 solution Indole capped Benzene-1,3,5-azadiene network −5.68 polymer cross-linked with ammonium persulfate Indole capped Benzene-1,3,5-azadiene network −5.501 polymer cross-linked with iron chloride Benzene-1,4-methyl azadiene polymer 57 kohms −6.02/−2.64 3.38 film

Example 2

A polyazine polymer of furan 2,5-azadiene was synthesized as follows. 0.2 g of furan 2,5-dicarboxaldehyde was reacted with 30 μl of hydrazine monohydrate (65%) in 15 ml of ethanol to yield the furan 2,5-azadiene polymer (Scheme 6).

This polymer was further modified by the addition of indole or pyrrole moieties on the ends of the polymer chain by reacting the ethanol washed polymer (0.05 g) with 0.05 g of indole-5-carboxaldehyde or 0.05 g of pyrrole-2-carboxaldehyde and 12 μl of hydrazine monohydrate (65%) in 5 ml of acetonitrile to yield indole or pyrrole capped polymers respectively. These polymers were subsequently crosslinked into networked lattices by reacting with an excess of 0.8 M ammonium persulfate. FIG. 5 shows the indole capped 2,5 azadiene polymer polymer (bottom) and the final networked indole capped polymer after oxidation (top).

Example 3

An indole capped 1,3,5-benzene azadiene networked polymer was prepared. 0.25 g of 1,3,5-tricarbox-aldehyde was reacted with 100 μl of hydrazine monohydrate (65%) in 10 ml of acetonitrile. To this mixture 1 g of 5-carboxyindole was added to terminate the polymerization reaction while capping the polymer chain extensions. FIG. 6A shows the synthesis of an indole capped benzene-1,3,5-azadiene network polymer, which was subsequently reacted with either ammonium persulfate or FeCl₃ oxidizing agents to crosslink the indoles, thereby producing an indole crosslinked benezene 1,3,5-azadiene network polymer. The polymer shifted from a white milky colloidal solution to a deep red/black precipitate upon oxidative cross-linking as shown in FIG. 6B upon oxidation of the polymer with ammonium persulfate. FIG. 6C shows an absorption spectrum for the oxidized cross-linked indole capped 1,3,5-benzene azadiene polymer. Absorption spectrum was determined by dissolving the soluble portion of the oxidized polymer in dimethylformamide and reading absorbance on a Shimadzu UV/Vis mini 1240 from 180 nm to 1100 nm. Cyclic voltammetery was performed to determine HOMO, LUMO and bandgap for the polymer (FIG. 6D). The polymer was heat evaporated onto a glassy carbon electrode and cyclic voltammetry was performed to measure orbital energy levels with a Bio-Logic SP-150 potentiostat using a silver/silver chloride reference electrode, platinum counter electrode, and a glassy carbon working electrode. Potentials were referenced with respect to ferrocene. The working solution was degassed under argon with 0.1 M tetrabutylammonium hexafluorophospate in acetonitrile as the supporting electrolyte. Potentials were measured in solution and also as thin films where possible.

Example 4

Multifunctional organic substrates were synthesized as set forth in Table 3.

TABLE 3 Dimer cross-linking substrates. Reactant 1 Reactant 2 Solvent Product Indole-3-carboxaldehyde Hydrazine Ethanol Indole-3-azadiene Indole-5-carboxaldehyde Hydrazine Ethanol Indole-5-azadiene Pyrrole-3-carboxaldehyde Hydrazine Ethanol Pyrrole-3-azadiene Thianaphthene-3- Hydrazine Ethanol Thianaphthene-3- carboxaldehyde azadiene FIG. 7 shows (from top to bottom) the synthesis of the 3-indole azadiene, thianaphthene-3-azadiene, 5-indole azadiene, and 3-pyrrole azadiene.

The foregoing is illustrative of the present invention, and is not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the claims to be included therein. All publications, patent applications, patents, patent publications, and other references cited herein are incorporated by reference in their entireties for the teachings relevant to the sentence and/or paragraph in which the reference is presented. 

1. A method of preparing a cross-linked polyazine polymer, comprising: reacting an organic substrate with a multiamine to form an organic polymer, wherein the organic substrate comprises a substituted moiety selected from the group consisting of tetrahydronaphthyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, pyrazinyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone, and the organic substrate is substituted with at least two aldehydes and/or ketones; and oxidizing said organic polymer to form said cross-linked polyazine polymer.
 2. The method of claim 1, wherein said oxidizing step is carried out by enzymatic oxidative polymerization.
 3. The method of claim 2, wherein said enzymatic polymerization is carried out using an oxidase selected from the group consisting of a phenol oxidase, a polyphenol oxidase, a catechol oxidase, a tyrosinase, a laccase, and any combination thereof.
 4. The method of claim 1, wherein said oxidizing step is carried out by chemical oxidative polymerization with an oxidizing agent. 5.-7. (canceled)
 8. The method of claim 1, wherein said moiety is substituted with said at least two aldehydes and/or ketones.
 9. (canceled)
 10. The method of claim 1, wherein said organic substrate comprises at least three aldehydes and/or ketones.
 11. The method of claim 1, wherein said multiamine is selected from the group consisting of hydrazine, triaminobenzene, and any combination thereof.
 12. The method of claim 1, wherein said cross-linked polyazine polymer is a heteropolymer.
 13. The method of claim 1, further comprising reacting said organic polymer with a second organic substrate comprising at least two aldehydes and/or ketones and a multiamine, prior to said oxidizing step.
 14. The method of claim 1, further comprising reacting a monocarbonyl compound with said organic polymer and a multiamine to form a capped organic polymer, prior to said oxidizing step.
 15. The method of claim 14, wherein said monocarbonyl compound has the structure

wherein R is a conjugated moiety; and R¹ is selected from the group consisting of hydrogen, alkyl, and alkenyl.
 16. The method of claim 1, wherein said organic substrate has the structure

wherein R is a conjugated moiety selected from the group consisting of tetrahydronaphthyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, pyrazinyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone; and R¹ and R² each independently selected from the group consisting of hydrogen, alkyl, and alkenyl.
 17. The method of claim 1, wherein said organic substrate has the structure

wherein R is a conjugated moiety selected from the group consisting of tetrahydronaphthyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, pyrazinyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone; and R¹, R², and R³ are each independently selected from the group consisting of hydrogen, alkyl, and alkenyl.
 18. The method of claim 1, wherein said organic substrate comprises a metal.
 19. An electrochemical device comprising: a working electrode; a counter electrode; and said networked polyazine polymer of claim 1, wherein said working electrode is in operative communication with said counter electrode, and said cross-linked polyazine polymer is in operative communication with said working electrode or said counter electrode.
 20. The electrochemical device of claim 19, wherein said cross-linked polyazine polymer is disposed on a least a portion of the working electrode.
 21. The electrochemical device of claim 19, wherein the electrochemical device is a battery, a fuel cell, a capacitor or a device formed of a combination thereof, a supercapacitor, an ultracapacitor, or an electric double-layer capacitor. 22.-26. (canceled)
 27. The method of claim 1, wherein said cross-linked polyazine polymer comprises a portion having the structure —C═N—N═C— or —C═N—R—N═C—, wherein R comprises said substituted moiety. 